CN114210351A - Catalyst for synthesizing vinyl sulfate and vinyl sulfate synthesis method - Google Patents
Catalyst for synthesizing vinyl sulfate and vinyl sulfate synthesis method Download PDFInfo
- Publication number
- CN114210351A CN114210351A CN202111641513.7A CN202111641513A CN114210351A CN 114210351 A CN114210351 A CN 114210351A CN 202111641513 A CN202111641513 A CN 202111641513A CN 114210351 A CN114210351 A CN 114210351A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- vinyl sulfate
- carrier
- ruthenium trichloride
- filtrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of vinyl sulfate synthesis, and discloses a catalyst for vinyl sulfate synthesis and a vinyl sulfate synthesis method, wherein the catalyst comprises the following steps: preparing water, a ruthenium trichloride carrier catalyst and a buffer solution according to a proportion, adding ethylene sulfite, dropwise adding a sodium hypochlorite solution, keeping the temperature and performing suction filtration to obtain a filter cake consisting of the ethylene sulfate and the ruthenium trichloride carrier catalyst and a filtrate containing sodium chloride; 2/3, directly applying the filtrate with the volume of 2/3 to the next batch, and concentrating and crystallizing the 1/3 filtrate to obtain a byproduct sodium chloride; adding an organic solvent into the filter cake to dissolve the vinyl sulfate, and carrying out solid-liquid separation to obtain a ruthenium trichloride carrier catalyst filter cake and a filtrate containing the vinyl sulfate; washing the filter cake, drying in vacuum and directly applying to the next batch; and (4) carrying out phase separation, washing, drying, concentration and crystallization on the filtrate to obtain a finished product of the vinyl sulfate. The invention solves the problems of difficult recovery of the catalyst ruthenium trichloride, high raw material cost and large wastewater amount in the prior art.
Description
Technical Field
The invention relates to the field of synthesis of vinyl sulfate, and particularly relates to a catalyst for synthesizing vinyl sulfate and a vinyl sulfate synthesis method.
Background
The vinyl sulfate is an SEI film forming additive, is used as an additive of lithium ion battery electrolyte, and has the functions of inhibiting the reduction of the initial capacity of the battery, increasing the initial discharge capacity, reducing the expansion of the battery after high-temperature placement, and improving the charge and discharge performance and cycle number of the battery. The vinyl sulfate can be used for synthesizing a drug intermediate by using an organic synthesized hydroxyethylation reagent, and can also be used for synthesizing a certain heterocyclic compound for gelatin hardening, an antihypertensive drug and a raw material of a novel double-surfactant. The vinyl sulfate has wider and wider application and larger market demand.
At present, the synthesis method of the vinyl sulfate mainly comprises the following steps: acylation, substitution, addition, dioxane synthesis, and direct oxidation. Currently, the method commonly used in industry is to use sodium hypochlorite as an oxidant and oxidize the sodium hypochlorite under the catalysis of ruthenium trichloride and the like as catalysts to obtain the vinyl sulfate. The method generates a large amount of salt-containing wastewater, and the used noble metal catalyst ruthenium trichloride is difficult to recycle. Ruthenium is an extremely expensive rare noble metal and is expensive, so that the synthesis process of vinyl sulfate is very high in cost. At present, no recycling method of catalyst ruthenium trichloride in the vinyl sulfate synthesis process exists at home and abroad, and no report about the reuse of filtrate in the reaction is found. Therefore, the reduction of wastewater and the recycling of the ruthenium catalyst in the vinyl sulfate synthesis process are the key points of whether the process can realize large-scale industrial production and can be popularized and applied.
Disclosure of Invention
The invention aims to provide a catalyst for synthesizing vinyl sulfate and a vinyl sulfate synthesis method, so as to realize waste water reduction and ruthenium catalyst recycling in the vinyl sulfate synthesis process.
In order to achieve the purpose, the invention adopts the following technical scheme: a catalyst for synthesizing vinyl sulfate is a ruthenium trichloride carrier catalyst, and the carrier is gas-phase SiO2、γ-Al2O3Shell activated carbon, ZrO2、CeO2HY-5 and HZSM-5.
The technical scheme also provides a vinyl sulfate synthesis method, which comprises the following steps:
step I: preparing water, a ruthenium trichloride carrier catalyst and a buffer solution according to a proportion, adding ethylene sulfite, dropwise adding a sodium hypochlorite solution with the mass concentration of 7.5-13%, and then preserving heat;
step II: after the heat preservation is finished, carrying out suction filtration to obtain a filter cake consisting of the vinyl sulfate and the ruthenium trichloride carrier catalyst and a filtrate containing sodium chloride;
step III: in the filtrate containing sodium chloride, 2/3 volume of filtrate is directly applied to the next batch, 2/3 mass of sodium bicarbonate solid is added, and the rest 1/3 filtrate is concentrated and crystallized to obtain a byproduct sodium chloride;
step IV: adding an organic solvent into a filter cake consisting of the vinyl sulfate and the ruthenium trichloride carrier catalyst to dissolve the vinyl sulfate, and then carrying out solid-liquid separation again to obtain a ruthenium trichloride carrier catalyst filter cake and a filtrate containing the vinyl sulfate; washing the filter cake, drying in vacuum, and directly applying to the next batch after drying in vacuum; and (4) carrying out phase separation, washing, drying, concentration and crystallization on the filtrate to obtain a finished product of the vinyl sulfate.
The principle and the advantages of the scheme are as follows: in the technical scheme, based on the consideration of the recovery purpose of the catalyst, the carrier catalyst is designed, the carrier catalyst can be recycled compared with the existing homogeneous catalyst, the existing homogeneous catalyst is catalysts such as ruthenium trichloride and lanthanum trichloride, the homogeneous catalyst is generally dissolved in water or an organic solvent and is in an ionic state, the homogeneous catalyst can not be recovered in waste water after the reaction is finished, and the carrier catalyst is recovered and recycled by suction filtration and drying after the solid-state reaction is finished, so that the production cost is greatly saved. In designing the supported catalyst, the support is selected based on: firstly, the sodium hypochlorite does not react with any one of the raw materials and the products; secondly, the carrier has strong enough adsorption capacity and interaction force to ruthenium ions; ③ the carrier is insoluble in water or organic solvent. The carriers listed above can meet the above requirements, wherein the effects of gamma-aluminum oxide and shell activated carbon are better, but the sodium hyposulfite solution can change the shell activated carbon into a finer particle, and the color of the mother liquor is darker after the reaction is finished, which is not beneficial to the recovery treatment of wastewater, so the effect of aluminum oxide is best. In addition, part of the mother liquor after the reaction is finished is supplemented with part of sodium bicarbonate buffer salt solid, and the pH value of the mother liquor is adjusted to 6-7, so that the cyclic utilization of the mother liquor is realized.
1. The novel process for synthesizing the vinyl sulfate by catalyzing the ruthenium trichloride supported catalyst solves the problems of difficult recovery of the ruthenium trichloride catalyst and high raw material cost in the existing process route, and the recovered catalyst can be applied for at least 6 times, so that the use cost of the catalyst is greatly reduced.
2. The vinyl sulfate synthesis process provided by the invention can realize the recycling of the filtrate 2/3, and greatly reduces the generation of waste water.
3. The ruthenium trichloride supported catalyst provided by the invention is simple to prepare, stable in product yield in the process of mechanically applying, simple in process condition, easy to operate, low in cost and easy to realize large-scale industrial production.
Preferably, as an improvement, the loading amount of the ruthenium trichloride is 2-8% of the mass of the carrier.
In the technical scheme, the active components with overlarge loading capacity are not uniformly distributed and have weaker binding capacity with the carrier, the loss of the overloaded active components of the carrier is serious, and the circulation frequency of the catalyst is reduced; the too small loading capacity is not enough to support the consumption of the active components required by the reaction, the reaction effect is poor, and the loading capacity is a better range verified by tests.
Preferably, as a modification, the method is obtained by an equal volume impregnation method.
In the technical scheme, the isovolumetric impregnation method is a common catalyst preparation method, and the method has the advantages of simple operation, easy industrialization, convenient control of the content of active components in the preparation process and capability of omitting the step of filtering redundant impregnation liquid.
Preferably, as a modification, the equal-volume impregnation method comprises the following steps:
s1, pretreatment of the carrier: the carrier is heated to 300-550 ℃ by a program in a muffle furnace, and is roasted for 3-5h at the constant temperature of 300-550 ℃;
s2, measuring the water absorption amount of the carrier;
s3, preparing a solution: according to the carrier loading capacity and the water absorption capacity, preparing a dilute hydrochloric acid solution of ruthenium trichloride with a certain concentration;
s4, dipping: mixing a carrier and a prepared dilute hydrochloric acid solution of ruthenium trichloride, quickly stirring until the carrier is wet and sticky, and then standing at room temperature;
s5, drying and grinding.
In the technical scheme, the preparation process of the carrier catalyst is simple in process and easy to popularize and apply practically, and in addition, the carrier is optimized in the early stage, so that the carrier and the active component have a synergistic effect in the roasting stage.
Preferably, as an improvement, in the step I, the addition amount of the ruthenium trichloride supported catalyst is 1-5% of the mass of the ethylene sulfite.
In the technical scheme, the dosage of the catalyst has great influence on the catalytic effect, the reaction is not thorough due to the excessively low dosage of the catalyst, unnecessary waste is caused due to the excessively high dosage of the catalyst, and the dosage of the catalyst is in a better range verified by tests.
Preferably, as an improvement, in the step I, the temperature is controlled to be 0-15 ℃ when the ethylene sulfite is dripped; the heat preservation condition is that the temperature is preserved for 1-2 min at 0-15 ℃.
In the technical scheme, when the temperature is too high, the product vinyl sulfate can be decomposed, and when the heat preservation time is too long, the product can also be decomposed; when the temperature is too low, the reaction system is an aqueous solution, and the phenomenon of peripheral icing can be generated.
Preferably, as an improvement, in the step I, the molar ratio of the sodium hypochlorite to the ethylene sulfite in the sodium hypochlorite solution is 1:1 to 2: 1.
In the technical scheme, the molar ratio of sodium hypochlorite to ethylene sulfite is optimized, unnecessary resource waste can be caused by overhigh molar ratio, and incomplete reaction can be caused by overlow molar ratio.
Preferably, as a modification, in step IV, the solvent for dissolving the vinyl sulfate filter cake is one of ethyl acetate, dichloromethane, dichloroethane, dimethyl carbonate, dioxane, ethanol or methanol.
In the technical scheme, the ethyl acetate, the dichloromethane, the dichloroethane, the dimethyl carbonate, the dioxane, the ethanol and the methanol can effectively dissolve the ethylene sulfate, and are all commercial finished products, the sources are wide and easy to obtain, and the application technology is mature.
Preferably, as an improvement, in the step IV, the vacuum drying condition is that the temperature is 100-350 ℃, and the drying time is 3-5 h.
In the technical scheme, the vacuum drying condition is optimized, and the active components on the carrier are aggregated when the drying temperature is too high and the drying time is too long; the drying temperature is too low, the drying time is too short, the combination of the carrier and the active component is not firm enough, and the loss of the active component is quick.
Drawings
FIG. 1 shows γ -Al in the examples of the present invention2O3The application effect of the ruthenium trichloride catalyst which is a carrier is shown in the figure.
FIG. 2 is a gas chromatogram of the finished product of vinyl sulfate.
Detailed Description
The following is a detailed description of the embodiments, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the following embodiments are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; the materials, reagents and the like used are all commercially available.
A catalyst for synthesizing vinyl sulfate is a ruthenium trichloride carrier catalyst, and the preparation method comprises the following steps:
s1, pretreatment of the carrier: taking a certain amount of carrier, heating to 550 ℃ by a program in a muffle furnace, and roasting for 3 hours at the constant temperature of 550 ℃; the carrier of the supported catalyst is gas-phase SiO2、γ-Al2O3Shell activated carbon, ZrO2、CeO2One or a mixture of two of HY-5 and HZSM-5;
s2, determination of water absorption capacity of carrier: accurately weighing 1.0000g of carrier, dropwise adding deionized water, and stirring to obtain 1.0g of optimal carrier wet sticky state, namely the water absorption capacity of the carrier is 1.0 mL/g;
s3, preparing a solution: accurately weighing 0.78g RuCl3·3H2Dissolving the O solid in 15mL of 10% dilute hydrochloric acid solution to prepare dilute hydrochloric acid solution of ruthenium trichloride;
s4, dipping: weighing 15g of roasted carrier in a beaker, adding the solution prepared in S3, quickly stirring for 30min until the carrier is wet and sticky, and standing at room temperature for 4 h;
s5, drying and grinding: and (3) placing the well-placed sample in a vacuum drying oven, carrying out vacuum drying for 24h at the temperature of 150 ℃, and then grinding the sample by agate for a long time to obtain powder, thus obtaining the ruthenium trichloride carrier catalyst.
A vinyl sulfate synthesis method adopts a ruthenium trichloride carrier catalyst as a reaction catalyst, and comprises the following steps:
step I: adding 450g of process water, 1g of carrier catalyst with the loading capacity of 4% and 125g of sodium bicarbonate buffer solution (the mass concentration is 5%) into a 1000mL four-neck flask with mechanical stirring in sequence, stirring, cooling to 5 ℃, adding 50g of ethylene sulfite, dropwise adding 300g of sodium hypochlorite solution with the effective chlorine concentration of 13% at the temperature of 0-5 ℃, controlling the dropwise adding time within 40min, and preserving heat for 2min after the dropwise adding is finished.
Step II: after the heat preservation is finished, quickly performing suction filtration to obtain a filter cake consisting of the vinyl sulfate and the ruthenium trichloride carrier catalyst and a filtrate containing sodium chloride;
step III: the 2/3 volume amount of the filtrate containing sodium chloride is directly applied to the next batch, 2/3 mass of sodium bicarbonate solid is added, and the rest 1/3 is concentrated and crystallized to obtain a byproduct sodium chloride;
step IV: adding 400g of dichloromethane into a filter cake consisting of the vinyl sulfate and the ruthenium trichloride carrier catalyst, dissolving, and then performing suction filtration again to obtain a ruthenium trichloride carrier catalyst filter cake and a filtrate containing the vinyl sulfate. Washing the filter cake with water, and vacuum-drying at 150 ℃ for 4h, and directly applying to the next batch after drying; the filtrate is subjected to phase separation, washing, drying, concentration and crystallization to obtain a finished product of the vinyl sulfate, and the finished product of the vinyl sulfate is subjected to gas chromatography detection, wherein the result is shown in figure 2, and the gas chromatography shows that the purity of the vinyl sulfate product obtained by the scheme reaches 99.9%.
Repeating the steps for multiple times to complete the recycling of the catalyst.
The first experimental example: test of catalyst application times of different carriers
And (3) experimental design: the difference of each supported catalyst is only the difference of the carriers, the specific design of each experimental group and the application times of the catalyst when synthesizing the vinyl sulfate are shown in table 1, wherein the application times are the reaction times.
TABLE 1 number of catalyst applications for different supports
| Number of implementation | Carrier | Number of times of application |
| Examples 1 to 5 | Gas phase SiO2 | 3 |
| Examples 6 to 9 | HY-5 | 2 |
| Examples 10 to 13 | HZSM-5 | 2 |
| Examples 14 to 21 | γ-Al2O3 | 7 |
| Examples 22 to 24 | CeO2 | 1 |
As can be seen from examples 1 to 24, the SiO is in the gas phase2、HY-5、HZSM-5、γ-Al2O3And CeO2Is used as a carrier, and is prepared into a carrier catalyst by adopting an isometric impregnation method, wherein gamma-Al2O3The effect is best, the catalyst can be stably used for 7 times, a graph of the using times and the yield of the vinyl sulfate product is shown in figure 1, the yield is relatively stable, the abscissa is the using times of the catalyst, and the ordinate is the yield of the product, so that the gram number of pure vinyl sulfate is obtained.
Experiment example two: different loading of RuCl3/γ-Al2O3Catalyst testing
With RuCl3/γ-Al2O3The preparation method of the catalyst is the same as that of the catalyst, only the catalyst loading capacity is adjusted during the synthesis of the vinyl sulfate, the yield and the content of the finished vinyl sulfate product are detected, the detection method is gas chromatography, and the design and the results of each test group are shown in tables 2, 3 and 4. Respectively adopting RuCl with active component loading of 2%, 4% and 8%3/γ-Al2O3The catalyst was reacted (three replicates) with a RuCl loading of 4%3/γ-Al2O3The catalyst has good effect, the active component has poor dispersibility when the loading capacity is low, the reaction effect is poor, and the loading capacity is lowWhen the concentration is too high, the active components are aggregated, the interaction with the carrier is weak, and the loss of the active components is quick.
TABLE 22% RuCl3/γ-Al2O3Results of catalyst reaction
TABLE 34% RuCl3/γ-Al2O3Results of catalyst reaction
TABLE 48% RuCl3/γ-Al2O3Results of catalyst reaction
Experiment example three: testing of different amounts of Supported catalyst
With RuCl3/γ-Al2O3The preparation method of the catalyst is the same as that of the catalyst, only the dosage of the catalyst is adjusted during the synthesis of the vinyl sulfate, the yield and the content of the finished product of the vinyl sulfate are detected, the detection method is gas chromatography, and the design and the result of each test group are shown in table 5. The catalyst dosage is changed, when the catalyst dosage is less, the reaction yield is lower, the reaction yield tends to be stable along with the increase of the catalyst dosage, and the optimal dosage of the catalyst is selected to be 2 percent in consideration of economic saving.
TABLE 5 test results for different amounts of supported catalyst
The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (10)
1. A catalyst for vinyl sulfate synthesis, characterized in that: the catalyst is ruthenium trichloride carrier catalyst, and the carrier is gas phase SiO2、γ-Al2O3Shell activated carbon, ZrO2、CeO2HY-5 and HZSM-5.
2. The catalyst for vinyl sulfate synthesis according to claim 1, characterized in that: the loading capacity of the ruthenium trichloride is 2-8% of the mass of the carrier.
3. The catalyst for vinyl sulfate synthesis according to claim 2, characterized in that: obtained by an isovolumetric immersion method.
4. The catalyst for vinyl sulfate synthesis according to claim 3, characterized in that: the equal-volume impregnation method comprises the following steps:
s1, pretreatment of the carrier: heating the carrier to 300-550 ℃ in a muffle furnace by a program, and roasting at the constant temperature of 300-550 ℃ for 3-5 h;
s2, measuring the water absorption amount of the carrier;
s3, preparing a solution: according to the carrier loading capacity and the water absorption capacity, preparing a dilute hydrochloric acid solution of ruthenium trichloride with a certain concentration;
s4, dipping: mixing a carrier and a prepared dilute hydrochloric acid solution of ruthenium trichloride, quickly stirring until the carrier is wet and sticky, and then standing at room temperature;
s5, drying and grinding.
5. A process for synthesizing vinyl sulfate, characterized in that the supported ruthenium trichloride catalyst according to any one of claims 1 to 4 is used as a reaction catalyst, comprising the steps of:
step I: preparing water, a ruthenium trichloride carrier catalyst and a buffer solution according to a proportion, adding ethylene sulfite, dropwise adding a sodium hypochlorite solution with the mass concentration of 7.5-13%, and then preserving heat;
step II: after the heat preservation is finished, carrying out suction filtration to obtain a filter cake consisting of the vinyl sulfate and the ruthenium trichloride carrier catalyst and a filtrate containing sodium chloride;
step III: in the filtrate containing sodium chloride, 2/3 volume of filtrate is directly applied to the next batch, 2/3 mass of sodium bicarbonate solid is added, and the rest 1/3 filtrate is concentrated and crystallized to obtain a byproduct sodium chloride;
step IV: adding an organic solvent into a filter cake consisting of the vinyl sulfate and the ruthenium trichloride carrier catalyst to dissolve the vinyl sulfate, and then carrying out solid-liquid separation again to obtain a ruthenium trichloride carrier catalyst filter cake and a filtrate containing the vinyl sulfate; washing the filter cake, drying in vacuum, and directly applying to the next batch after drying in vacuum; and (4) carrying out phase separation, washing, drying, concentration and crystallization on the filtrate to obtain a finished product of the vinyl sulfate.
6. The vinyl sulfate synthesis method according to claim 5, wherein: in the step I, the addition amount of the ruthenium trichloride carrier catalyst is 1-5% of the mass of the ethylene sulfite.
7. The vinyl sulfate synthesis method according to claim 6, wherein: in the step I, the temperature is controlled to be 0-15 ℃ when the ethylene sulfite is dripped; the heat preservation condition is that the temperature is preserved for 1-2 min at 0-15 ℃.
8. The vinyl sulfate synthesis method according to claim 7, wherein: in the step I, the molar ratio of sodium hypochlorite to ethylene sulfite in the sodium hypochlorite solution is 1: 1-2: 1.
9. The vinyl sulfate synthesis method according to claim 8, wherein: in the step IV, the solvent for dissolving the vinyl sulfate filter cake is one of ethyl acetate, dichloromethane, dichloroethane, dimethyl carbonate, dioxane, ethanol or methanol.
10. The vinyl sulfate synthesis method according to claim 9, wherein: in the step IV, the vacuum drying condition is that the temperature is 100-350 ℃, and the drying time is 3-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111641513.7A CN114210351B (en) | 2021-12-29 | 2021-12-29 | Catalyst for synthesizing vinyl sulfate and method for synthesizing vinyl sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111641513.7A CN114210351B (en) | 2021-12-29 | 2021-12-29 | Catalyst for synthesizing vinyl sulfate and method for synthesizing vinyl sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114210351A true CN114210351A (en) | 2022-03-22 |
| CN114210351B CN114210351B (en) | 2023-06-30 |
Family
ID=80706759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111641513.7A Active CN114210351B (en) | 2021-12-29 | 2021-12-29 | Catalyst for synthesizing vinyl sulfate and method for synthesizing vinyl sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114210351B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116351413A (en) * | 2023-02-24 | 2023-06-30 | 无锡威孚环保催化剂有限公司 | Catalyst for synthesizing vinyl sulfate and preparation method of vinyl sulfate |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6277982B1 (en) * | 1999-08-20 | 2001-08-21 | Isis Pharmaceuticals, Inc. | Alkylation of alcohols, amines, thiols and their derivatives by cyclic sulfate intermediates |
| CN1785511A (en) * | 2005-11-22 | 2006-06-14 | 清华大学 | Ru/Al2O3 catalytic ozone oxidation catalyst and its microwave synthesis method |
| CN101322947A (en) * | 2008-08-07 | 2008-12-17 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
| CN101584988A (en) * | 2009-03-30 | 2009-11-25 | 浙江工业大学 | Bi-component composite type metallic catalyst and application thereof |
| CN105214687A (en) * | 2015-10-16 | 2016-01-06 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of propane low-temperature catalytic oxidation carried noble metal ruthenium catalyst and preparation |
| CN105481826A (en) * | 2016-01-11 | 2016-04-13 | 烟台海川化学制品有限公司 | Preparation method of ethylene sulfate |
| CN106554268A (en) * | 2015-09-24 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of method of aqueous catalysis synthesizing methyl succinic acid |
| CN106631762A (en) * | 2015-10-30 | 2017-05-10 | 中国科学院大连化学物理研究所 | Method for preparing pyrovinic acid through catalysis of itaconic acid for hydrogenation by ruthenium carbon catalyst after carbon thermal reduction |
| CN111215060A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation of supported platinum group metal monatomic catalyst and application thereof in deoxidation reaction |
| CN111909129A (en) * | 2020-09-03 | 2020-11-10 | 常熟市常吉化工有限公司 | Method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide |
| CN112209914A (en) * | 2020-10-21 | 2021-01-12 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing vinyl sulfate by adopting micro-flow field reaction technology |
| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
-
2021
- 2021-12-29 CN CN202111641513.7A patent/CN114210351B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6277982B1 (en) * | 1999-08-20 | 2001-08-21 | Isis Pharmaceuticals, Inc. | Alkylation of alcohols, amines, thiols and their derivatives by cyclic sulfate intermediates |
| CN1785511A (en) * | 2005-11-22 | 2006-06-14 | 清华大学 | Ru/Al2O3 catalytic ozone oxidation catalyst and its microwave synthesis method |
| CN101322947A (en) * | 2008-08-07 | 2008-12-17 | 福州大学 | Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof |
| CN101584988A (en) * | 2009-03-30 | 2009-11-25 | 浙江工业大学 | Bi-component composite type metallic catalyst and application thereof |
| CN106554268A (en) * | 2015-09-24 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of method of aqueous catalysis synthesizing methyl succinic acid |
| CN105214687A (en) * | 2015-10-16 | 2016-01-06 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of propane low-temperature catalytic oxidation carried noble metal ruthenium catalyst and preparation |
| CN106631762A (en) * | 2015-10-30 | 2017-05-10 | 中国科学院大连化学物理研究所 | Method for preparing pyrovinic acid through catalysis of itaconic acid for hydrogenation by ruthenium carbon catalyst after carbon thermal reduction |
| CN105481826A (en) * | 2016-01-11 | 2016-04-13 | 烟台海川化学制品有限公司 | Preparation method of ethylene sulfate |
| CN111215060A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation of supported platinum group metal monatomic catalyst and application thereof in deoxidation reaction |
| CN111909129A (en) * | 2020-09-03 | 2020-11-10 | 常熟市常吉化工有限公司 | Method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide |
| CN112209914A (en) * | 2020-10-21 | 2021-01-12 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing vinyl sulfate by adopting micro-flow field reaction technology |
| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
Non-Patent Citations (2)
| Title |
|---|
| JANINA OKAL·LESZEK KEPINSKI: "Sintering of Colloidal Ru/γ-Al2O3 catalyst in Hydrogen", CATAL LETT, vol. 128, pages 331 - 336, XP019671985 * |
| 闫春生 等: "硫酸乙烯酯的合成", 河南化工, vol. 35, pages 22 - 24 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116351413A (en) * | 2023-02-24 | 2023-06-30 | 无锡威孚环保催化剂有限公司 | Catalyst for synthesizing vinyl sulfate and preparation method of vinyl sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114210351B (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110201703A (en) | A kind of preparation method of multi-element metal doping nitridation carbon composite | |
| CN110813359B (en) | Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof | |
| CN110756203B (en) | Ni2P/Mn0.3Cd0.7S photocatalytic water splitting composite catalyst and preparation method and application thereof | |
| CN113368843B (en) | Strontium titanate supported palladium catalyst for CL-20 synthesis and preparation application thereof | |
| CN114210351B (en) | Catalyst for synthesizing vinyl sulfate and method for synthesizing vinyl sulfate | |
| WO2024078051A1 (en) | Biomass skeleton carbon-metal composite micro-nano structure catalytic material, and preparation method and use | |
| CN113173605A (en) | Core-shell type metal sulfide composite material and preparation method and application thereof | |
| CN107399766B (en) | A kind of preparation method of spherical nickel cobalt manganese persursor material | |
| CN105268442A (en) | Copper-based methanol synthesis catalyst and preparation method therefor | |
| CN113171757B (en) | Carbon dioxide adsorbent and preparation method thereof | |
| CN116003262B (en) | Synthesis method of N, N-dimethylaniline | |
| CN105964267B (en) | A kind of Cu-series catalyst for synthesizing methanol and preparation method thereof | |
| CN115739004B (en) | Lithium-aluminum adsorption material prepared from salt lake brine with high magnesium-lithium ratio and method thereof | |
| CN114471727B (en) | Au@NH 2 MIL-125 (Cu/Ti) photocatalyst, and preparation method and application thereof | |
| WO2023273119A1 (en) | Method for preparing ru-based catalyst and use of ru-based catalyst | |
| CN114618440B (en) | Synthesis process of lithium salt adsorbent precursor | |
| CN1149552A (en) | Technology for producing high-purity active zinc oxide by ammonia water circulation complexation method | |
| CN114436893A (en) | Production process of deuterated acetonitrile | |
| CN111135874A (en) | Utilization method of waste alumina carrier | |
| CN113941322B (en) | Preparation method of alumina-coated transesterification catalyst | |
| CN117361584B (en) | Method for preparing sodium hexafluorophosphate for sodium battery by utilizing sodium hydrogen fluoride | |
| CN115849459B (en) | Preparation method and application of cobalt hydroxide | |
| CN115709073B (en) | Preparation method of tin-based catalyst and application of tin-based catalyst in catalyzing biomass sugar to prepare methyl lactate | |
| CN115634666B (en) | Method for preparing adsorbent by taking fly ash as raw material and application of adsorbent in separation of methane and nitrogen | |
| CN114426467B (en) | Method for preparing glutaraldehyde based on heterogeneous catalysis technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |